Baeyer-Villiger Oxidation
Follow-up reaction of Brown Hydroboration
Ozonolysis
Recent Literature
A clean and safe method for the dihydroxylation of alkenes under organic-solvent- and metal-free conditions was developed. The resin-supported sulfonic acid is easily recycled. Y. Usui, K. Sato, M. Tanaka, Angew. Chem. Int. Ed., 2003, 42, 5623-5625.
Convenient methods for the preparation of stable and non-volatile mono- and dichloroborane adducts of dioxane from dioxane-BCl3 and NaBH4 in the presence of catalytic amounts of tri- or tetraglyme were developed. The dioxane-monochloroborane adduct hydroborates representative olefins cleanly and rapidly and lead to the corresponding alcohols in quantitative yields after oxidation.
J. V. B. Kanth, H. C. Brown, J. Org. Chem, 2001, 66, 5359-5365.
A rhodium-catalyzed enantioselective syn addition of bis(catecholato)diboron to simple alkenes in the presence of (S)-Quinap provides enantioenriched 1,2-diols after subsequent oxidation. The substrate scope, the reaction mechanism, and competing pathways are discussed.
S. Trudeau, J. M. Morgan, M. Shrestha, J. P. Morken, J. Org. Chem., 2005, 70, 9538-9544.
Pt-catalyzed enantioselective addition of bis(pinacolato)diboron (B2(pin)2) to conjugated dienes enables an asymmetric 1,4-dihydroxylation of 1,3-dienes. Dienes which are unable to adopt the S-cis conformation are unreactive. For most substrates, 1,4-addition is the predominant pathway.
H. E. Burks, L. T. Kliman, J. P. Morken, J. Am. Chem. Soc., 2009, 131, 9134-9135.
Lithiated epoxides react stereospecifically with boronates to give syn-1,2-diols, a process that can be used iteratively to create triols containing four stereogenic centers.
E. Vedrenne, O. A. Wallner, M. Vitale, F. Schmidt, V. K. Aggarwal, Org. Lett., 2009, 11, 165-168.
A direct, mild ketohydroxylation of various 1-aryl-1-alkenes with H2O2, catalyzed by the inexpensive 12-tungstophosphoric acid/cetylpyridinium chloride system, gave acyloins in good yields and high regioselectivies.
Y. Zhang, Z. Shen, J. Tang, Y. Zhang, L. Kong, Y. Zhang, Org. Biomol. Chem., 2006, 4, 1478-1482.
An efficient epoxidation of a broad range of olefins using hydrogen peroxide as the oxidant has been accomplished in the presence of acetic acid and a manganese catalyst that exhibits an uncommon chemoselectivity.
I. Garcia-Bosch, X. Ribas, M. Costas, Adv. Synth. Catal., 2008, 351, 348-352.
A chiral bisaryl-silyl-protected pyrrolidine acts as a very selective epoxidation organocatalyst using simple oxidation agents. The scope of the reaction is demonstrated by the formation of optically active α,β-epoxy aldehydes in high yields and enantioselectivities. The asymmetric epoxidation reactions proceed also under environmental friendly reaction conditions in, for example, water mixtures of alcohols.
M. Marigo, J. Franzen, T. B. Poulsen, W. Zhuang, K. A. Jorgensen, J. Am. Chem. Soc., 2005, 127, 6284-6289.
An effective epoxidation of lipophilic alkenes using hydrogen peroxide was accomplished with a manganese sulfate/bicarbonate catalytic system in an ionic liquid at room temperature. K.-H. Tong, K.-Y. Wong, T. H. Chan, Org. Lett., 2003, 5, 3423-3425.
An epoxidation of alkenes using hydrogen peroxide as the terminal oxidant is promoted by catalytic amounts (1.0-0.1 mol %) of manganese(2) salts, and must be performed using at least catalytic amounts of bicarbonate buffer. Various aryl-substituted, cyclic, and trialkyl-substituted alkenes were epoxidized under these conditions using 10 equiv of hydrogen peroxide, but monoalkyl-alkenes were not. Additives such as sodium acetate and salicylic acid enhanced the rate of the desired epoxidation reaction by 2-3 times. Possible mechanisms for the reaction are discussed.
B. S. Lane, M. Vogt, V. J. DeRosa, K. Burgess, J. Am. Chem. Soc., 2002, 124, 11946-11954.
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Aryl benzyl selenoxides are efficient catalysts for the epoxidation of various olefinic substrates and the Baeyer-Villiger oxidation of aldehydes and ketones with hydrogen peroxide. M. A. Goodman, M. R. Detty, Synlett, 2006, 1100-1104.
A highly enantioselective catalytic epoxidation of α,β-unsaturated diaryl enones was achieved with high chemical yield by using aqueous hydrogen peroxide in the presence of a
guanidine-urea bifunctional organocatalyst. The catalyst performs cooperatively by interaction of the guanidine group with hydrogen peroxide and the urea group with the enone or vice versa.
S. Tanaka, K. Nagasawa Synlett, 2009, 667-670.
Chiral primary amine salts catalyze highly enantioselective epoxidations of cyclic enones with hydrogen peroxide.
X. Wang, C. M. Reisinger, B. List, J. Am. Chem. Soc., 2008, 130, 6070-6071.
M. A. Goodman, M. R. Detty, Synlett, 2006, 1100-1104.
Aldehydes undergo oxidative transformation to the methyl esters in methanol as solvent upon treatment with catalytic amounts of vanadium pentoxide in combination with hydrogen
peroxide. This method features mild reaction conditions, short reaction times, high efficiencies, cost-effectiveness, and facile isolation of the desired products. R. Gopinath, B. Patel, Org. Lett., 2000, 2, 577-579.
A convenient and efficient oxidation of hydroxylated and methoxylated benzaldehydes and acetophenones to the corresponding phenols uses hydrogen peroxide and methyltrioxorhenium as catalyst in ionic liquids [bmim]BF4 and [bmim]PF6. R. Bernini, A. Coratti, G. Provenzano, G. Fabrizi, D. Tofani, Tetrahedron, 2005, 61, 1821-1825.
In the presence of catalytic amounts of phosphomolybdic acid (PMA), ethereal hydrogen peroxide reacted readily with a range of epoxides at ambient temperature, giving corresponding β-hydroxyhydroperoxides in good yields. Y. Li, H.-D. Hao, Y. Wu, Org. Lett., 2009, 11, 2691-2694.
Nitroso arenes are prepared in good yield from anilines by oxidation with H2O2 catalysed with MoO3/KOH, ammonium molybdate or other molybdenum salts. Further oxidation to nitro arenes is also described.
A. Defoin, Synthesis, 2004, 706-710.
A versatile procedure oxidizes sulfanes to sulfoxides without any overoxidation to sulfones using a combination of hydrogen peroxide and triflic acid. This method tolerates oxidatively sensitive functional groups.
M. M. Khodaei, K. Bahrami, A. Karimi, Synthesis, 2008, 1682-1684.
Various aromatic and aliphatic sulfides are selectively oxidized to sulfoxides and sulfones in good to excellent yields using 30% H2O2 in the presence of a recyclable silica-based tungstate interphase catalyst at room temperature.
B. Karimi, M. Ghoreishi-Nezhad, J. H. Clark, Org. Lett., 2005, 7, 625-628.
Sc(OTf)3 is an efficient catalyst for the hydrogen peroxide mediated monooxidation of alkyl-aryl sulfides and methyl cysteine containing peptides. The method is high yielding, compatible with many widely used protecting groups, suitable for solid-phase applications and proceeds with minimum over-oxidation.
M. Matteucci, G. Bhalay, M. Bradley, Org. Lett., 2003, 5, 235-237.
An air and moisture tolerant complex of Ti(IV) with a C3-symmetric triphenolate amine ligand efficiently catalyzes sulfoxidation reactions at room temperature without previous activation using aqueous hydrogen peroxide as oxidant.
M. Mba, L. J. Prins, G. Licini, Org. Lett., 2007, 9, 21-24.
The combination of very high ee values with high yield, the consequence of an efficient initial asymmetric oxidation followed by an efficient kinetic resolution, makes the reported system very practical for the asymmetric oxidation of simple akyl aryl sulfides.
C. Drago, L. Caggiano, R. F. W. Jackson, Angew. Chem. Int. Ed., 2005, 44, 7221-7223.
A chiral Fe(salan) complex serves as an efficient catalyst for asymmetric oxidation of sulfides using hydrogen peroxide in water without surfactant. Not only alkyl aryl sulfides but also various methyl alkyl sulfides were oxidized to the corresponding sulfoxides with high enantioselectivities.
H. Egami, T. Katsuki, J. Am. Chem. Soc., 2007, 129, 8940-8941.
The asymmetric oxidation of sulfides to chiral sulfoxides with hydrogen peroxide in good yield and high enantioselectivity has been catalyzed very effectively by a chiral vanadium-salan complex. The efficient kinetic resolution of racemic sulfoxides catalyzed by the vanadium-salan system is also described.
J. Sun, C. Zhu, Z. Dai, M. Xang, Y. Pan, H. Hu, J. Org. Chem., 2004, 69, 8500-8503.
The combination of H2O2 and SOCl2 is a highly reactive reagent for the direct oxidative conversion of thiol derivatives to the corresponding sulfonyl chlorides through oxidative chlorination. Upon reaction with amines, the corresponding sulfonamides were obtained in excellent yields in very short reaction times.
K. Bahrami, M. M. Khodaei, M. Soheilizad, J. Org. Chem., 2009, 74, 9287-9291.
Hydrogen peroxide, in the presence of zirconium tetrachloride, is a very efficient reagent for the direct oxidative conversion of thiols and disulfides into the corresponding sulfonyl chlorides with high purity through oxidative chlorination. Excellent yields, very short reaction times, mild reaction conditions, and the avoidance of harsh reagents are the main advantages of this method.
K. Bahrami, M. M. Khodaei, M. Soheilizad, Synlett, 2009, 2773-2776.
Thiols were effectively oxidized into disulfides by reacting with hydrogen peroxide in the presence of a catalytic amount of iodide ion or iodine.
M. Kirihara, Y. Asai, S. Ogawa, T. Noguchi, A. Hatano, Y. Hirai, Synthesis, 2007, 3286-3289.
Simple, mild, and environmentally friendly procedures for the direct conversion of dithioesters into either carboxylic acids or esters using hydrogen peroxide under alkaline conditions are described.
F. Grellepois, C. Portella, Synthesis, 2008, 3443-3446.
The hydrogen peroxide-zirconium(IV) chloride reagent system is efficient and general for the conversion of thioamides to amides in short reaction times and good chemoselectivity, and allows a simple workup that precludes the use of toxic solvents. K. Bahrami, M. M. Khodaei, Y. Tirandaz, Synthesis, 2009, 369-371.
The synthesis of a planar-chiral bisflavin catalyst (1) and its use in asymmetric Bayer-Villiger-Oxidations is described.
S. Murahashi, S. Ono, Y. Imada, Angew. Chem. Int. Ed., 2002, 41, 2366-2368.
α-Acetoxylation of ketones catalyzed by iodobenzene using^acetic anhydride and 30% aqueous hydrogen peroxide as the oxidant is an effective and economical method for the preparation of α-acetoxy ketones in good yields.
J. Sheng, Y. Li, M. Tang, B. Gao, G. Huang, Synthesis, 2007, 1165-1168.
Ketones or ketals were readily converted into the corresponding gem-dihydroperoxides in high yields by treatment with ethereal H2O2 at ambient temperature in the presence of phosphomolybdic acid (PMA) as catalyst.
Y. Li, H.-D. Hao, Q. Zhang, Y. Wu, Org. Lett., 2009, 11, 1615-1618.
1-Arylethanones and related compounds are rapidly brominated in dioxane with the H2O2-HBr aq system, resulting in the replacement of two hydrogen atoms in the methyl group with bromine. The reaction is also accompanied by bromination of the aromatic ring provided that the latter contains electron-donating substituents.
A. O. Terent'ev, S. V. Khodykin, I. B. Krylov, Y. N. Ogibin, G. I. Nikishin, Synthesis, 2006, 1087-1092.
Active methylene compounds can be chemoselectively brominated in high yields using potassium bromide, hydrochloric acid, and hydrogen peroxide at room temperature.
M. Kirihara, S. Ogawa, T. Noguchi, K. Okubo, Y. Monma, I. Shimizu, R. Shimosaki, A. Hatano, Y. Hirai, Synlett, 2006, 2287-2289.
Pd-catalyzed enantioselective diborations of prochiral allenes followed by allylation reactions with primary imines provide vinyl boronates which may be oxidized to give nonracemic Mannich products. Alternatively, enantiomerically enriched homoallylic amine derivatives may be obtained by protonation and Suzuki cross-coupling of the vinyl boronate. J. D. Sieber, J. P. Morken, J. Am. Chem. Soc., 2006, 128, 74-75.
A simple, mild and efficient procedure cleaves a wide range of ketoximes and aldoximes to the corresponding carbonyl compounds in an aqueous medium using catalytic amounts of potassium bromide and ammonium heptamolybdate tetrahydrate in combination with hydrogen peroxide.
N. C. Ganguly, S. K. Barik, Synthesis, 2008, 425-428.
A selective and efficient oxidative iodination of electron rich arenes was carried out with one equivalent of KI and two equivalents of 30% hydrogen peroxide in MeOH in the presence of strong acid.
J. Iskra, S. Stavber, M. Zupan, Synthesis, 2004, 1869-1873.
A convenient method for the synthesis of 2-substituted benzimidazoles and benzothizoles offers short reaction times, large-scale synthesis, easy and quick isolation of the products, excellent chemoselectivity, and excellent yields as main advantages. K. Bahrami, M. M. Khodaei, F. Naali, J. Org. Chem., 2008, 73, 6835-6837.
A simple and efficient procedure for the synthesis of substituted benzimidazoles through a one-pot condensation of o-phenylenediamines with aryl aldehydes in the presence of H2O2 and HCl in acetonitrile at room temperature features short reaction time, easy and quick isolation of the products, and excellent yields.
K. Bahrami, M. M. Khodaei, I. Kavianinia, Synthesis, 2007, 417-427.
A simple protocol for the deprotection of 1,3-dithianes and 1,3-dithiolanes showed tolerance for a number of phenol and amino protecting groups using 30% aqueous hydrogen peroxide activated by iodine catalyst (5 mol%) in water in the presence of sodium dodecyl sulfate (SDS)
under essentially neutral conditions without any detectable overoxidation. N. G. Ganguly, S. K. Barik, Synthesis, 2009, 1393-1399.
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